Phosphorus and calcium collection method, and mixture produced by said collection method

ABSTRACT

An aqueous solution containing 30 ppm or more of carbon dioxide is brought into contact with a steel-making slag to elute phosphorus and calcium contained in the steel-making slag into the aqueous solution. Subsequently, carbon dioxide is removed from the aqueous solution to precipitate a mixture comprising a phosphorus compound and a calcium compound. In this manner, a mixture comprising a phosphorus compound and a calcium compound and containing phosphorus in an amount of 1% by mass or more in terms of phosphorus atom content can be produced.

TECHNICAL FIELD

The present invention relates to a method of recovering phosphorus andcalcium from steelmaking slag, and a mixture obtained by the recoverymethod.

BACKGROUND ART

It has been known that steelmaking slag produced in steelmaking process(e.g., converter slag, pretreatment slag, secondary refining slag andelectric furnace slag) contains oxides of phosphorus, calcium, iron,silicon, manganese, aluminum, and magnesium, for example. Specifically,steelmaking slag contains phosphorus with calcium silicates such asCa₂SiO₄ and Ca₃SiO₅, and calcium iron oxides such as Ca₂Fe₂O₅.Steelmaking slag contains calcium, from quicklime (CaO) loaded duringsteelmaking process, as undissolved CaO (free lime), or as Ca(OH)₂ orCaCO₃ generated from free lime reacting with moisture or carbon dioxidein the air.

Phosphorus is an important element as the material for fertilizers orchemical products. Mineral phosphorus (phosphorus) is not produced inJapan, and imported in the form of mineral phosphorus, fertilizers,chemical products, for example. High-quality mineral phosphorus is lowin quantity, which may cause strain on phosphorus resources; therefore,the phosphorus price is now on the rise (see, e.g., NPLs 1 and 2). Inview of such a situation, when phosphorus can be recovered from thesteelmaking slag, the strain on phosphorus resources would bealleviated. Thus, attempts to recover phosphorus from steelmaking slaghave been made (see, e.g., PTLS 1 and 2).

PTL 1 discloses a method of recovering phosphorus from steelmaking slagwith calcium removed. In the recovery method, calcium is removed fromsteelmaking slag by washing the steelmaking slag with water containingcarbon dioxide. Next, phosphorus in the steelmaking slag is eluted intoa mineral acid by dipping the steelmaking slag in the mineral acid.Lastly, phosphorus (phosphoric acid) is recovered by neutralizing themineral acid containing eluted phosphorus (extract).

PTL 2 discloses a method in which a calcium compound from steelmakingslag for more than one times, and phosphorus in a state of solidsolution in a specific calcium compound is recovered. In the recoverymethod, the steelmaking slag (pretreatment slag) is dipped in watercontaining dissolved carbon dioxide. Subsequently, a calcium compoundhaving no phosphorus in a state of solid solution is eluted, and then, acalcium compound having phosphorus in a state of solid solution iseluted, whereby solution containing phosphorus is recovered fromdephosphorization slag.

Calcium is also an important element which is used in a sinteringprocess for iron-making in the form of calcium carbonate, or used in asteelmaking process in the form of calcium oxide after calcined. Calciumhydroxide obtained by slaking calcium oxide with water is used as aneutralizer for acids and the like in a draining process. Therefore,when calcium can be recovered from steelmaking slag obtained iniron-making process, calcium can be reused to reduce iron-making costs.Thus, attempts to recover calcium from steelmaking slag have been made(see PTL 3).

PTL 3 discloses a method of recovering calcium from converter slag usingcarbon dioxide. The recovery method elutes calcium from the converterslag by injecting water into the converter slag. Then, calcium (calciumcarbonate) is recovered from the converter slag by keeping the lowerlimit of pH at about 10.

CITATION LIST Patent Literature

PTL 1

-   Japanese Patent Application Laid-Open No. 2010-270378    PTL 2-   Japanese Patent Application Laid-Open No. 2013-142046    PTL 3-   Japanese Patent Application Laid-Open No. 55-100220

Non-Patent Literature

NPL 1

-   “Mineral Resources Material Flow 2011” Japan Oil, Gas and Metals    National Corporation, May 2012, P405-410    NPL 2-   Kazuyo Matsubae et al., “Recovery of Artificial Phosphorus Resource    from Wastes” Collection of Sociotechnology Research Papers,    Sociotechnology Research Network, March 2008, p106-113

SUMMARY OF INVENTION Technical Problem

The method of recovering phosphorus disclosed in PTL 1 uses a mineralacid and neutralizer thereby disadvantageously increasing recoverycosts. A filtering apparatus (filter) is also needed to filterundissolved materials at the time of dipping steelmaking slag in themineral acid, thereby increasing recovery costs. Furthermore, othercomponents such as iron, manganese, magnesium, silicon, aluminum andcalcium are also dissolved in the mineral acid, and those components areprecipitated even when the extract is neutralized.

The method of recovering phosphorus disclosed in PTL 2 needs to dissolvea calcium compound for more than one times, which complicates recoveryprocess, and increases recovery costs.

In the method of recovering phosphorus disclosed in PTL 3, keeping pH at10 or more is difficult in practical use, and when pH becomes lower,precipitated calcium carbonate is dissolved again. When the lower limitof pH is kept at about 10, the precipitation amount becomes low.Furthermore, dissolving calcium silicates containing phosphorus isdifficult in the recovery method, and little phosphorus can berecovered, thereby increasing recovery costs.

As described above, the conventional methods for recovering phosphorusor calcium suffer from high recovery costs.

An object of the present invention is to provide a method of recoveringphosphorus and calcium, which can recover phosphorus and calcium fromsteelmaking slag at low cost. Another object of the present invention isto provide a mixture containing phosphorus and calcium obtained by therecovery method.

Solution to Problem

The present inventors have found that the objects can be achieved bybringing steelmaking slag in contact with aqueous solution containingcarbon dioxide, and precipitating eluted substances by removing carbondioxide from the aqueous solution, and completed the present inventionwith further studies.

The present invention relates to a recovery method as follows.

[1] A method of recovering phosphorus and calcium from steelmaking slag,comprising: bringing the steelmaking slag in contact with aqueoussolution containing 30 ppm or more of carbon dioxide to elute phosphorusand calcium contained in the steelmaking slag into the aqueous solution;and subsequently, removing the carbon dioxide from the aqueous solutionto precipitate a mixture containing a phosphorus compound and a calciumcompound.

[2] The method of recovering phosphorus and calcium according to [1],wherein the removing of the carbon dioxide includes: partly removing thecarbon dioxide from the aqueous solution to precipitate the mixture; andsubsequently, further removing the carbon dioxide from the aqueoussolution to precipitate the mixture, and a proportion of the phosphoruscompound in the mixture obtained in the further removing of the carbondioxide is less than a proportion of the phosphorus compound in themixture obtained in the partly removing of the carbon dioxide.

[3] The method of recovering phosphorus and calcium according to [2],wherein a precipitation rate of the mixture in the partly removing ofthe carbon dioxide is 0.1 g/min·L or less.

[4] The method of recovering phosphorus and calcium according to any oneof [1] to [3], wherein, in the removing of the carbon dioxide, thecarbon dioxide is removed by blowing one or more gases selected from thegroup consisting of air, nitrogen, oxygen, hydrogen, argon and heliuminto the aqueous solution.

[5] The method of recovering phosphorus and calcium according to [4],wherein, in the partly removing of the carbon dioxide, the one or moregases are intermittently blown into the aqueous solution.

[6] The method of recovering phosphorus and calcium according to any oneof [1] to [3], wherein, in the removing of the carbon dioxide, thecarbon dioxide is removed by reducing a pressure of the aqueoussolution.

[7] The method of recovering phosphorus and calcium according to any oneof [1] to [3], wherein, in the removing of the carbon dioxide, thecarbon dioxide is removed by heating the aqueous solution.

The present invention also relates to a mixture obtained by the abovemethods.

[8] The mixture obtained by the method of recovering phosphorus andcalcium according to any one of [1] to [7], wherein the mixture containsa phosphorus compound and a calcium compound, and the mixture contains 1wt % or more of phosphorus in terms of atom

Advantageous Effects of Invention

According to the present invention, phosphorus and calcium can berecovered from steelmaking slag at low cost.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart of a method of recovering phosphorus and calciumaccording to an embodiment of the present invention;

FIG. 2 is a flowchart of a method of recovering phosphorus and calciumaccording to another embodiment of the present invention; and

FIG. 3 is a flowchart of a method of recovering phosphorus and calciumin Experiment 5.

DESCRIPTION OF EMBODIMENTS

Recovery Method

FIG. 1 is a flowchart of a method of recovering phosphorus and calciumaccording to an embodiment of the present invention. As illustrated inFIG. 1, the method of recovering phosphorus and calcium according to theembodiment includes a first step in which phosphorus and calcium insteelmaking slag are eluted into an aqueous solution containing carbondioxide, and a second step which is to be performed after the first stepand in which a mixture containing a phosphorus compound and a calciumcompound is precipitated.

(First Step)

In the first step, steelmaking slag is brought in contact with aqueoussolution containing carbon dioxide to elute phosphorus and calciumcontained in the steelmaking slag into the aqueous solution.

Steelmaking slag as the material is prepared, and then fractured orpulverized (Step S100). The types of steelmaking slag are notparticularly limited as long as the steelmaking slag contains phosphorusand calcium. Examples of steelmaking slag include converter slag,pretreatment slag, secondary refining slag and electric furnace slag.Typically, steelmaking slag contains, for example, compounds (oxides) ofphosphorus (P), calcium (Ca), iron (Fe), silicon (Si), manganese (Mn),magnesium (Mg), and aluminum (Al). Phosphorus is contained with calciumsilicates, which are composite oxides of calcium and silicon, such asCa₂SiO₄ and Ca₃SiO₅. Calcium is contained as calcium oxide (CaO), whichis free lime, calcium hydroxide (Ca(OH)₂) or calcium carbonate (CaCO₃).

Steelmaking slag may be used as discharged in a steelmaking process, butit is preferable that steelmaking slag is used, which is fractured orpulverized and then from which metal iron is removed. When steelmakingslag discharged in a steelmaking process is used without any treatment,a recovery operation may become complicated. The maximum particlediameter of the steelmaking slag is preferably, although not limited to,1000 μm or less. When the maximum particle diameter of the steelmakingslag is more than 1000 μm, the contact area between the steelmaking slagand the aqueous solution is small that the time for eluting phosphorusand calcium becomes longer, which lengthens the time for recovery ofphosphorus and calcium. An example of a method of pulverizing thesteelmaking slag is, although not limited to, to pulverize thesteelmaking slag with, e.g., a roller mill or ball mill.

Next, phosphorus and calcium in the steelmaking slag prepared in stepS100 is eluted into the aqueous solution containing carbon dioxide bybringing the steelmaking slag in contact with the aqueous solutioncontaining carbon dioxide (Step S110).

The types of aqueous solution containing carbon dioxide are notparticularly limited as long as the aqueous solution contains 30 ppm ormore of carbon dioxide, and may contain other components. Any method maybe used for dissolving carbon dioxide into water. For example, carbondioxide can be dissolved in water by allowing gas containing carbondioxide to bubble (blowing). The gas to be blown may contain componentsother than carbon dioxide. The gas to be blown may contain oxygen ornitrogen, for example. A discharged gas after combustion, or mixed gasof carbon dioxide, air and moisture may be blown to allow carbon dioxideto dissolve. The gas to be blown preferably contains carbon dioxide inhigh concentration (e.g. 90%) to accelerate reactions and increaseelution of a calcium compound (calcium silicate). As described above,the concentration of carbon dioxide in the aqueous solution is 30 ppm ormore. When the concentration of carbon dioxide in the aqueous solutionis 30 ppm or more, phosphorus and calcium in the steelmaking slag can beeluted in the aqueous solution containing carbon dioxide. Since carbondioxide in the aqueous solution decreases as phosphorus and calciumdissolve, carbon dioxide needed to be provided further into the aqueoussolution after the steelmaking slag is brought in contact with theaqueous solution to keep the concentration of carbon dioxide (30 ppm ormore) which is necessary for elution of phosphorus and calcium into theaqueous solution.

Any method may be used for bringing the steelmaking slag in contact withthe aqueous solution containing carbon dioxide. For example, thesteelmaking slag may be dipped in water in which carbon dioxide ispreviously dissolved, or the steelmaking slag may be dipped in water andthen carbon dioxide is dissolved in the water. While the steelmakingslag is in contact with the aqueous solution, it is preferable that thesteelmaking slag and the aqueous solution are stirred to acceleratereactions. The steelmaking slag from which phosphorus and calcium havebeen eluted contains a higher iron component content, thus thesteelmaking slag can be used as iron-making materials without anytreatment or after subjected to a treatment such as magnetic separation.

When the steelmaking slag is brought in contact with the aqueoussolution containing carbon dioxide, calcium oxide (CaO), calciumhydroxide (Ca(OH)₂), calcium carbonate (CaCO₃), calcium silicates(Ca₂SiO₄ and Ca₃SiO₅), and calcium iron oxides (e.g., Ca₂Fe₂O₅) in thesteelmaking slag react with water containing carbon dioxide whereby acalcium component is eluted into the aqueous solution. When calciumsilicates are dissolved, diphosphorus pentaoxide (P₂O₅) in thesteelmaking slag reacts with the aqueous solution containing carbondioxide whereby a phosphorus component is eluted into water. Phosphorusand calcium contained in the steelmaking slag are thus eluted into theaqueous solution containing carbon dioxide by bringing the steelmakingslag in contact with the aqueous solution.

Subsequently, the aqueous solution containing dissolved phosphorus andcalcium (supernatant) and the steelmaking slag are separated by, e.g.,filtration (Step S120).

(Second Step)

In the second step subsequent to the first step, a mixture containingthe phosphorus compound and calcium compound is precipitated from theaqueous solution containing dissolved phosphorus and calcium, and themixture is recovered.

The mixture containing the phosphorus compound and calcium compound isprecipitated by removing carbon dioxide from the aqueous solutioncontaining dissolved phosphorus and calcium. Any method may be used forremoving carbon dioxide from the aqueous solution. Examples of themethods for removing carbon dioxide include (1) blowing gas into theaqueous solution, (2) reducing the pressure of the aqueous solution, and(3) heating the aqueous solution. The methods will be describedindividually.

(1) Blowing Gas into Aqueous Solution

In the method of removing carbon dioxide by blowing gas into the aqueoussolution, gas other than carbon dioxide is blown into the aqueoussolution. This easily removes carbon dioxide from the aqueous solutionby replacing dissolved carbon dioxide with the blown gas. The type ofgas to be blown into water is preferably an inorganic gas having lowreactivity with water, or an organic gas having low reactivity withwater. Examples of inorganic gases include air, nitrogen, oxygen,hydrogen, argon and helium. Examples of the organic gases includemethane, ethane, ethylene, acetylene and propane. Organic gases need tobe handled carefully since they may combust or explode when leakedoutside. When gases reactive with water such as chlorine gas and sulfurdioxide gas were used, ions such as chlorine ion and sulfate ion aregenerated in water. Those ions form salts with calcium eluted in water,which is not preferable because no mixture containing a phosphoruscompound and a calcium compound precipitates when carbon dioxide isremoved from the aqueous solution.

(2) Reducing Pressure of Aqueous Solution

In the method of removing carbon dioxide by reducing the pressure of theaqueous solution, the aqueous solution is put into an airtight containerand air in the container is evacuated using, e.g., a pump to allow thecontainer to have a reduced-pressure atmosphere (degassing). In additionto reducing the pressure of the aqueous solution, ultrasonic waves maybe applied to the aqueous solution, or the aqueous solution may bestirred. Furthermore, in addition to reducing the pressure of theaqueous solution, ultrasonic waves and stirring may be applied to theaqueous solution. This can effectively remove carbon dioxide from theaqueous solution.

(3) Heating Aqueous Solution

In the method of removing carbon dioxide by heating the aqueoussolution, the temperature of the aqueous solution is elevated. To lowerheating costs, the temperature is preferably elevated to a temperaturewithin a range so that the vapor pressure of water does not exceed thepressure in the atmosphere. For example, when the pressure in theatmosphere is the atmospheric pressure (1 atm), the heating temperatureis less than 100° C.

When the aqueous solution is heated, not only carbon dioxide is removedbut also a calcium compound is easily precipitated because the calciumcompound (calcium carbonate) becomes less soluble.

The above three methods (1) to (3) may be combined to remove carbondioxide. This can effectively remove carbon dioxide from the aqueoussolution. The most suitable combination can be selected in view of, forexample, a delivery system of gas or heat, a site location, and/oravailability of by-product gas in a factory.

For example, while gas is blown into the aqueous solution, air isevacuated more than the blowing gas amount to allow the pressure to be areduced-pressure atmosphere. In such a combination, provided are effectsof blowing gas which removes carbon dioxide and provides stirring, andof reducing the pressure of the aqueous solution which removes carbondioxide. Thus, carbon dioxide can be effectively removed. Additionally,heating can further accelerate removal of carbon dioxide. Carbon dioxidecan be easily removed by effects of blowing gas into the aqueoussolution and reducing the pressure of the aqueous solution, andtherefore, the heating temperature does not need to be high, which canreduce heating costs.

When carbon dioxide is removed from the aqueous solution, calcium in theaqueous solution precipitates as a calcium compound. Examples of theprecipitated calcium compounds include calcium carbonate, calciumhydrogen carbonate and calcium hydroxide. Phosphorus in the aqueoussolution is also precipitated as a phosphorus compound by removingcarbon dioxide from the aqueous solution. Examples of the precipitatedphosphorus compounds include calcium phosphate, calcium hydrogenphosphate and hydroxyapatite (HAp).

Subsequently, the mixture containing a phosphorus compound and a calciumcompound, which is precipitated in step S130, is recovered (Step S140).

By the above steps, phosphorus and calcium can be recovered fromsteelmaking slag at low cost.

As described above, the phosphorus compound recovered from steelmakingslag is important as phosphorus resources. Therefore, it is preferablethat the phosphorus compound content in the mixture is large. Thecalcium compound recovered from the steelmaking slag can be reused asiron-making materials. It is not preferable when the iron-makingmaterials contain a phosphorus compound. Therefore it is preferable toseparately obtain a mixture containing a large content of phosphoruscompound, and a mixture containing a small content of phosphoruscompound from the aqueous solution containing phosphorus and calcium. Toseparately obtain two mixtures having different contents of eachcompound, it is preferable to carry out the second step as follows.

FIG. 2 is a flowchart of a method of recovering phosphorus and calciumaccording to another embodiment of the present invention. As illustratesin FIG. 2, the second step in the present embodiment includes a thirdstep in which part of carbon dioxide is removed from aqueous solution toprecipitate a mixture, and a fourth step which is to be performed afterthe third step and in which carbon dioxide is further removed from theaqueous solution to precipitate a mixture. The proportion of aphosphorus compound contained in the mixture obtained in the fourth stepis less than that of the mixture obtained in the third step.

The same as described above are the fracturing or pulverizingsteelmaking slag (Step S100), the elution of phosphorus and calcium fromthe steelmaking slag (Step 110), separating aqueous solution containingdissolved phosphorus and calcium (supernatant) from the steelmaking slagfrom which phosphorus and calcium are eluted (Step S120).

(Third Step)

In the third step, a mixture with a high phosphorus compound content isprecipitated by removing part of carbon dioxide from aqueous solutioncontaining dissolved phosphorus and calcium (Step S230). The third steputilizes the nature of calcium compounds and phosphorus being easilyprecipitated together. The precipitation rate of the mixture in thethird step is preferably 0.1 g/min·L or less. When the precipitationrate is 0.1 g/min·L or less, a phosphorus compound adsorbs on thesurface of the calcium compound, which allows a large amount of thephosphorus compound to precipitate with the calcium compound. Stirringthe aqueous solution accelerates precipitation of the phosphoruscompound and calcium compound together. Subsequently, the mixture with ahigh phosphorus compound content is recovered (Step S240).

(Fourth Step)

In the fourth step subsequent to the third step, a mixture isprecipitated by further removing carbon dioxide from the aqueoussolution containing dissolved phosphorus and calcium (Step S250).Specifically, after the third step, the rest of the calcium compound isprecipitated by further removing carbon dioxide from the aqueoussolution. Since most of the phosphorus compound is precipitated in thethird step, a mixture with a low phosphorus compound content can beobtained. The method of removing carbon dioxide may be any one of theabove described blowing gas into the aqueous solution, reducing thepressure of the aqueous solution, and heating the aqueous solution. Anyone of the methods can obtain a calcium compound containing littlephosphorus compound. Subsequently, the mixture with a low phosphoruscompound content is recovered (Step S260).

The above steps can separately obtain the mixture with a high phosphoruscompound content and the mixture with a low phosphorus compound content.

In the third step, intermittingly removing carbon dioxide can alsoobtain a mixture with a high phosphorus content. Specifically, removingcarbon dioxide and suspending the removal of carbon dioxide, within ashort time, are repeated. In the present embodiment, carbon dioxide ispreferably removed by blowing gas into the aqueous solution or reducingthe pressure of the aqueous solution from the view point ofoperationality. For example, blowing gas into the aqueous solution for0.5 minutes and suspending the gas blowing into the aqueous solution forone minute are repeated for three times. This allows phosphorus toadsorb on the surface of a precipitated calcium compound, then a calciumcompound to newly precipitate on the surface of phosphorus or in thesolution, and then a phosphorus compound to newly adsorb on the surface,which enables a large amount of phosphorus compound to adsorb per unitvolume. In the third step, the stirring is preferably continued for sometime after the blowing of gas into the aqueous solution or reducing thepressure of the aqueous solution is stopped. This enables an unadsorbedphosphate compound to adsorb to the precipitated calcium compound. Theblowing of gas into the aqueous solution or reducing the pressure of theaqueous solution may be stopped at any time in the third step. Whencarbon dioxide is removed under specific conditions, the time of thethird step is preferably 1/50 to ⅓ of the total removal time of carbondioxide.

[Precipitate]

Thus obtained mixture (mixture according to the present invention)contains a phosphorus compound and a calcium compound, and the mixturecontains 1 wt % or more of phosphorus in terms of atom. As describedabove, the examples of the phosphorus compounds include calciumphosphate, calcium hydrogen phosphate and hydroxyapatite (HAp). Theexamples of the calcium compounds include calcium carbonate, calciumhydrogen carbonate and calcium hydroxide. The phosphorus content in themixture can be measured by ICP-AES method.

The method of recovering phosphorus and calcium can recover phosphorusand calcium from steelmaking slag as a mixture of a phosphorus compoundand a calcium compound at low cost by bringing aqueous solutioncontaining 30 ppm or more of carbon dioxide into contact with thesteelmaking slag, eluting phosphorus and calcium in the steelmaking slagin the aqueous solution, and removing carbon dioxide from the aqueoussolution.

Hereinafter, the present invention will be described in detail withreference to Examples, however, the present invention is not limited toExamples.

EXAMPLES Experiment 1

Experiment 1 shows examples in which each of removal of carbon dioxideand recovery of a mixture was carried out once.

1. Preparation of Slag

Two types of steelmaking slag each having a different component ratio(slag A and slag B) were prepared (see Table 1). Slag A and slag B werepulverized using a roller mill to have the maximum particle diameter of100 μm. The maximum particle diameter of the pulverized slag wasmeasured using a laser diffraction/scattering type particle sizedistribution measuring device.

TABLE 1 Component Ratio (wt %) Fe Ca Si Mn Mg Al P Slag A 14.0 35.1 7.13.7 1.6 2.3 0.8 Slag B 14.6 34.2 6.7 4.9 2.0 0.9 2.1

2. Elution of Phosphorus and Calcium

The pulverized slag (1 kg, 3 kg, or 5 kg) was loaded in 100 L of waterfilling each container to provide a slag suspension. Then the providedslag suspension was stirred using an impeller for 30 minutes whilecarbon dioxide is blown into the slag suspension at the rate of 20L/min. The carbon dioxide concentration at this time was 30 ppm or more.For the comparison, a slag suspension was stirred by an impeller for 30minutes without blowing carbon dioxide into the slag suspension. Eachslag suspension after stirring was allowed to stand to settle out slag.Then the supernatant was recovered and filtered by filtration underreduced pressure using a filter to remove floating substances.

3. Removal of Carbon Dioxide

Carbon dioxide contained in the supernatant was removed by one of thefollowing methods: (1) blowing gas into the aqueous solution, (2)reducing the pressure of the aqueous solution, (3) heating the aqueoussolution, (4) blowing gas into the aqueous solution and heating theaqueous solution, and (5) blowing gas into the aqueous solution,reducing the pressure of the aqueous solution and heating the aqueoussolution. A precipitate was generated in the supernatant by the method.The methods for removing carbon dioxide (the above (1) to (5)) will bedescribed.

(1) Blowing Gas into Aqueous Solution

The supernatant loaded in a container was stirred using an impeller for30 minutes while gas (air, N₂, O₂, H₂, Ar, He or a combination thereof)is blown into the supernatant at the rate of 20 L/min to remove carbondioxide. In Example 11 using N₂ and Ar as the gas, the rate of N₂ was 10L/min, and the rate of Ar was 10 L/min.

(2) Reducing Pressure of Aqueous Solution

For 30 minutes, ultrasonic waves were applied to the supernatant loadedin an airtight container while the inside pressure of the airtightcontainer was kept at 1/10 atm to remove carbon dioxide.

(3) Heating Aqueous Solution

The supernatant loaded in a container was stirred using an impeller for30 minutes while the liquid temperature of the supernatant is elevatedto 90° C. to remove carbon dioxide.

(4) Blowing Gas into Aqueous Solution and Heating Aqueous Solution

The supernatant loaded in a container was stirred using an impeller for30 minutes while air is blown into the supernatant at the rate of 20L/min, and the liquid temperature of the supernatant is elevated to 90°C. to remove carbon dioxide.

(5) Blowing Gas into Aqueous Solution, Reducing Pressure of AqueousSolution and Heating Aqueous Solution

A state was kept for 30 minutes to remove carbon dioxide, in which airis blown into the supernatant loaded in an airtight container at therate of 5 L/min while the inside pressure of the airtight container waskept at 3/10 atm, and the liquid temperature of the supernatant waselevated to 60° C.

4. Recovery of Mixture and Measurement of Phosphorus Concentration inMixture

Each supernatant containing a precipitate (mixture) was filtered underreduced pressure using a filter to recover the mixture. The supernatant,heated when removing carbon dioxide, was filtered under reduced pressureto recover the mixture while heating the supernatant so as not to lowerthe liquid temperature. The phosphorus concentration in the recoveredmixture was measured by ICP-AES method. The ICP-AES method confirmedthat the mixture also contains calcium. It was thus confirmed that amixture containing a phosphorus compound and a calcium compound wasobtained.

5. Results

Recovery conditions and recovery results of Experiment 1 are shown inTable 2.

TABLE 2 Removal Method of Carbon Dioxide Precipitate Slag PhosphorusEluting Amount Blowing Gas (Type of Gas) Reducing Concentration SlagMethod (kg/100 L) Air N₂ O₂ H₂ Ar He Pressure Heating Mass (g/L) (mass%) Ex. 1 A Water 1 Yes No No No No No No No 0.71 0.30 Ex. 2 Containing 3Yes No No No No No No No 1.79 0.43 Ex. 3 Dissolved 5 Yes No No No No NoNo No 2.25 0.35 Ex. 4 Carbon 1 No Yes No No No No No No 0.66 0.41 Ex. 5Dioxide 3 No Yes No No No No No No 1.38 0.39 Ex. 6 5 No Yes No No No NoNo No 1.99 0.45 Ex. 7 1 No No Yes No No No No No 0.89 0.29 Ex. 8 1 No NoNo Yes No No No No 0.70 0.38 Ex. 9 1 No No No No Yes No No No 0.88 0.29Ex. 10 1 No No No No No Yes No No 0.75 0.36 Ex. 11 1 No Yes No No Yes NoNo No 0.73 0.38 Ex. 12 1 No No No No No No Yes No 0.29 0.69 Ex. 13 1 NoNo No No No No No Yes 1.59 0.22 Ex. 14 1 Yes No No No No No No Yes 1.700.19 Ex. 15 1 Yes No No No No No Yes No 0.93 0.33 Ex. 16 1 No No No NoNo No Yes Yes 1.75 0.15 Ex. 17 1 Yes No No No No No Yes Yes 1.40 0.20Ex. 18 B 1 Yes No No No No No No No 0.79 0.67 Ex. 19 1 No Yes No No NoNo No No 0.86 0.70 Ex. 20 1 No No Yes No No No No No 0.88 0.61 Ex. 21 1No No No No No No Yes No 0.31 1.32 Ex. 22 1 No No No No No No No Yes1.92 0.41 Comp. A Water 1 Yes No No No No No No No 0.05 0.01 Ex. 1

As shown in Table 2, the recovery methods of Example 1 to 22 couldobtain a mixture containing a phosphorus compound and a calciumcompound, in which steelmaking slag is dipped in water containing carbondioxide, and then carbon dioxide is removed. On the other hand, therecovery method of Comparative Example 1 could hardly obtain a mixturecontaining a phosphorus compound and a calcium compound, in whichsteelmaking slag is dipped in water without carbon dioxide blown, andthen carbon dioxide is removed.

Experiment 2

Experiment 2 shows examples in which each of removal of carbon dioxideand recovery of a mixture was carried out twice.

1. Preparation of Slag

The same two types of steelmaking slag as Experiment 1 (slag A and slagB) were prepared.

2. Elution of Phosphorus and Calcium

The pulverized slag (1 kg, 3 kg, or 5 kg) was loaded in 100 L of waterfilling each container to provide a slag suspension. Then the providedslag suspension was stirred using an impeller for 30 minutes whilecarbon dioxide is blown into the slag suspension at the rate of 20 L/minEach slag suspension after stirring was allowed to stand to settle outslag, and then the supernatant was recovered and filtered by filtrationunder reduced pressure using a filter to remove floating substances.

3. Removal of Carbon Dioxide and Recovery of Mixture

(1) Blowing Gas into Aqueous Solution

The supernatant loaded in a container was stirred using an impeller for5 minutes while gas (air or N₂) is blown into the supernatant at therate of 20 L/min, and subsequently the gas blowing is suspended andstirring was continued for 5 minutes. The supernatant containing aprecipitate (mixture) was filtered under reduced pressure using a filterto recover the mixture. The supernatant after the recovery of themixture was loaded in the container again, and the supernatant wasstirred using the impeller for 25 minutes while gas (air or N₂) is blowninto the supernatant at the rate of 20 L/min. The supernatant containinga precipitate (mixture) was filtered under reduced pressure using afilter to recover the mixture.

(2) Reducing Pressure of Aqueous Solution

The inside pressure of an airtight container loaded with the supernatantwas kept at 1/10 atm for 5 minutes to remove carbon dioxide, and thenthe supernatant containing a precipitate (mixture) was filtered underreduced pressure using a filter to recover the mixture. The insidepressure of an airtight container which was again loaded with thesupernatant after the recovery of the mixture was kept at 1/10 atm for25 minutes to remove carbon dioxide, and the supernatant containing aprecipitate (mixture) was filtered under reduced pressure using a filterto recover the mixture.

4. Measurement of Phosphorus Concentration in Mixture

The phosphorus and calcium concentrations in the mixture were measuredin the same manner as in Experiment 1.

5. Results

Recovery conditions and recovery results of Experiment 2 are shown inTable 3.

TABLE 3 Precipitate Removal Time of Carbon Dioxide 0 to 5 min 5 to 30min Phosphorus Phosphorus Slag Amount Removal Method of ConcentrationConcentration Slag (kg/100 L) Carbon Dioxide Mass (g/L) (mass %) Mass(g/L) (mass %) Ex. 23 A 1 Air Blowing 0.08 3.17 0.79 0.01 Ex. 24 3 AirBlowing 0.13 5.32 1.7 0.01 Ex. 25 1 N₂ blowing 0.06 4.63 0.73 0.02 Ex.26 3 N₂ blowing 0.11 5.11 1.45 0.01 Ex. 27 1 Reducing Pressure 0.02 9.820.25 0.02 Ex. 28 B 1 Air Blowing 0.07 8.85 0.66 0.02 Ex. 29 1 N₂ blowing0.06 7.99 0.78 0.02

As shown in Table 3, first removal of carbon dioxide for short time (5minutes) could obtain a mixture with a high phosphorus content. Furtherremoval of carbon dioxide from the supernatant from which most ofphosphorus compound is removed could obtain a mixture with a lowphosphorus content.

Experiment 3

Experiment 3 shows examples in which each of two types of methods forremoving carbon dioxide mixture was carried out once to recover amixture.

1. Preparation of Slag and Elution of Phosphorus and Calcium

The same two types of steelmaking slag as Experiments 1 and 2 (slag Aand slag B) were prepared. Phosphorus and calcium were eluted in thesame procedure as in Experiment 2.

2. Removal of Carbon Dioxide

(1) Blowing Gas into Aqueous Solution and Heating Aqueous Solution

The supernatant loaded in a container was stirred using an impeller for5 minutes while gas (air or N₂) is blown into the supernatant at therate of 20 L/min, and then the supernatant containing a mixture wasfiltered under reduced pressure using a filter to recover the mixture.The supernatant after the recovery of the mixture was loaded in thecontainer again, and the supernatant was stirred using an impeller for25 minutes while the liquid temperature of the supernatant is elevatedto 90° C. to remove carbon dioxide. The supernatant was filtered underreduced pressure to recover a mixture while heating the supernatant soas not to lower the liquid temperature.

(2) Blowing Gas into Aqueous Solution and Reducing Pressure of AqueousSolution

The supernatant loaded in a container was stirred using an impeller for5 minutes while gas (air or N₂) is blown into the supernatant at therate of 20 L/min, and the supernatant containing a mixture was filteredunder reduced pressure using a filter to recover the mixture. Thesupernatant after the recovery of the mixture was loaded in an airtightcontainer again, the inside pressure of the airtight container was keptat 1/10 atm for 25 minutes to remove carbon dioxide, and then thesupernatant containing a mixture was filtered under reduced pressureusing a filter to recover the mixture.

3. Measurement of Phosphorus Concentration in Mixture

The phosphorus concentration in each mixture was measured in the samemanner as in Experiment 1.

4. Results

Recovery conditions and recovery results of Experiment 3 are shown inTable 4.

TABLE 4 Precipitate Removal Method of Reducing Pressure Carbon DioxideGas Blowing or Heating Slag Reducing Pressure Phosphorus PhosphorusAmount Gas Blowing or Heating Mass Concentration Mass Concentration Slag(kg/100 L) (0 to 5 min) (5 to 30 min) (g/L) (mass %) (g/L) (mass %) Ex.30 A 1 Air Blowing Heating 0.07 3.84 1.66 0.01 Ex. 31 3 Air BlowingHeating 0.12 5.58 2.29 0.01 Ex. 32 1 N₂ blowing Reducing Pressure 0.064.31 0.2 0.02 Ex. 33 3 N₂ blowing Heating 0.13 5.67 2.99 0.01 Ex. 34 B 1Air Blowing Heating 0.07 8.83 1.64 0.02

As shown in Table 4, first removal of carbon dioxide for short time (5minutes) could obtain a mixture with a high phosphorus content as inExperiment 2. Further removal of carbon dioxide from the supernatantfrom which most of phosphorus compound is removed could obtain a mixturewith a low phosphorus content.

Experiment 4

Experiment 4 shows examples in which one type of method of removingcarbon dioxide was carried out, and recovery of a mixture was carriedout twice.

1. Preparation of Slag and Elution of Phosphorus and Calcium

Slag A used in Experiments 1 and 2 was prepared. Phosphorus and calciumwere eluted in the same procedure as in Experiment 2. The weight ofloaded slag was 1 kg.

2. Removal of Carbon Dioxide

Carbon dioxide was removed by stirring a supernatant loaded in anairtight container using an impeller for 5 minutes while air is blowninto the supernatant at the predetermined rate, and subsequently the gasblowing is suspended and stirring was continued for 5 minutes.Subsequently, the supernatant containing a precipitate was filteredunder reduced pressure using a filter to recover the precipitate. Thencarbon dioxide was removed by stirring the supernatant loaded in thecontainer again using the impeller for 25 minutes while air is blowninto the supernatant at the predetermined rate, and subsequently thesupernatant containing a precipitate was filtered under reduced pressureusing a filter to recover the precipitate. The air blowing amount wasrepresented as the air volume for one minute at the atmospheric pressureper 1 L of the slag suspension.

3. Measurement of Phosphorus Concentration in Mixture

The phosphorus concentration in each mixture was measured in the samemanner as in Experiment 1.

4. Results

Recovery conditions and recovery results of Experiment 4 are shown inTable 5.

TABLE 5 Precipitate Removal Time of Carbon Dioxide Removal Method of 0to 5 min 5 to 30 min Carbon Dioxide Precipitation PhosphorusPrecipitation Phosphorus Air Blowing Amount Mass Rate Concentration MassRate Concentration (L/min) (g/L) (g/min · L) (mass %) (g/L) (g/min · L)(mass %) Ex. 35 0.20 0.07 0.014 3.34 0.70 0.028 0.01 Ex. 36 0.10 0.040.008 8.12 0.73 0.029 0.01 Ex. 37 0.05 0.02 0.003 14.60 0.81 0.032 0.02

As shown in Table 5, the precipitation rate of a phosphorus compound anda calcium compound being 0.1 g/min·L or less could increase thephosphorus compound content in a mixture.

Experiment 5

In Experiment 5, carbon dioxide was removed for multiple times (3times). FIG. 3 is a flowchart of a method of recovering phosphorus andcalcium in Experiment 5.

1. Preparation of Slag and Elution of Phosphorus and Calcium

Slag A used in Experiments 1 and 2 was prepared (Steps S100 and S110).Phosphorus and calcium were eluted in the same procedure as inExperiment 2 (Step S120). The weight of loaded slag was 1 kg.

2. Removal of Carbon Dioxide

Carbon dioxide was removed by stirring a supernatant loaded in acontainer using an impeller for 0.5 minutes while air is blown into thesupernatant at the predetermined rate, and subsequently the air blowingis suspended and stirring was continued for 1 minute. The gas blowingand suspending the gas blowing are repeated for three times (Steps S300and S310). A supernatant containing a mixture was filtered under reducedpressure using a filter to recover the mixture (Step S320).Subsequently, the supernatant loaded in a container again was stirredusing an impeller for 25 minutes while air is blown into the supernatantat the rate of 20 L/min (Step S330), and then the supernatant containinga mixture was filtered under reduced pressure using a filter to recoverthe mixture (Step S340).

3. Measurement of Phosphorus Concentration in Mixture

The phosphorus and calcium concentrations in the mixture were measuredin the same manner as in Experiment 1.

4. Results

Recovery conditions and recovery results of Experiment 5 are shown inTable 6.

TABLE 6 Removal of Carbon Dioxide for 3 Times Air Blowing (25 min)Precipitation Phosphorus Precipitation Phosphorus Mass RateConcentration Mass Rate Concentration (g/L) (g/min · L) (mass %) (g/L)(g/min · L) (mass %) Ex. 38 0.04 0.009 7.89 0.72 0.029 0.01

As shown in Table 6, intermittingly blowing gas (air) during the removalsteps of carbon dioxide could separately obtain a mixture with a highphosphorus compound content and a mixture with a low phosphorus compoundcontent.

As described above, the recovery method according to the presentinvention can recover phosphorus and calcium from steelmaking slag atlow cost by eluting phosphorus and calcium contained in the steelmakingslag into an aqueous solution containing carbon dioxide, andprecipitating a mixture containing a phosphorus compound and a calciumcompound.

This application claims priority based on Japanese Patent ApplicationNo. 2014-013536, filed on Jan. 28, 2014, the entire contents of whichincluding the specification and the drawings are incorporated herein byreference.

INDUSTRIAL APPLICABILITY

The method of recovering phosphorus and calcium of the present inventioncan recover phosphorus and calcium from steelmaking slag at low cost;therefore the method is particularly advantageous as a method ofrecovering phosphorus resources and calcium resources during ironmaking, for example.

The invention claimed is:
 1. A method of recovering phosphorus andcalcium from steelmaking slag, comprising: bringing the steelmaking slagin contact with an aqueous solution containing 30 ppm or more of carbondioxide to elute phosphorus and calcium contained in the steelmakingslag into the aqueous solution; subsequently, partly removing the carbondioxide from the aqueous solution to precipitate a first mixturecontaining a phosphorus compound in a phosphorous concentration of 3.17to 14.60 mass % and a calcium compound; and subsequently, furtherremoving the carbon dioxide from the aqueous solution to precipitate asecond mixture containing a phosphorus compound in a phosphorousconcentration of 0.01 to 0.02 mass % and a calcium compound.
 2. Themethod of recovering phosphorus and calcium according to claim 1,wherein a precipitation rate of the first mixture in the partly removingof the carbon dioxide is 0.1 g/min·L or less.
 3. The method ofrecovering phosphorus and calcium according to claim 1, wherein, in thepartly removing of the carbon dioxide and the further removing of thecarbon dioxide, the carbon dioxide is removed by blowing one or moregases selected from the group consisting of air, nitrogen, oxygen,hydrogen, argon and helium into the aqueous solution.
 4. The method ofrecovering phosphorus and calcium according to claim 3, wherein, in thepartly removing of the carbon dioxide, the one or more gases areintermittently blown into the aqueous solution.
 5. The method ofrecovering phosphorus and calcium according to claim 1, wherein, in thepartly removing of the carbon dioxide and the further removing of thecarbon dioxide, the carbon dioxide is removed by reducing a pressure ofthe aqueous solution.
 6. The method of recovering phosphorus and calciumaccording to claim 1, wherein, in the partly removing of the carbondioxide and the further removing of the carbon dioxide, the carbondioxide is removed by heating the aqueous solution.